CN104004146A - Urethane-organic silicon-acrylic ester ternary polymerization emulsion and preparation method thereof - Google Patents
Urethane-organic silicon-acrylic ester ternary polymerization emulsion and preparation method thereof Download PDFInfo
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- CN104004146A CN104004146A CN201410215289.9A CN201410215289A CN104004146A CN 104004146 A CN104004146 A CN 104004146A CN 201410215289 A CN201410215289 A CN 201410215289A CN 104004146 A CN104004146 A CN 104004146A
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Abstract
The invention discloses a urethane-organic silicon-acrylic ester ternary polymerization emulsion and a preparation method thereof. The preparation method comprises the following steps: A, modifying a polyurethane dispersion by using polyethersiloxanediol, and then carrying out end capping on the polyurethane dispersion through a (methyl) hydroxyethyl acrylate monomer to form an urethane-organic silicon-acrylic ester copolymer with both ends carried with unsaturated double bonds; and B, copolymerizing the obtained urethane-organic silicon-acrylic ester copolymer and an acrylic ester monomer to prepare the urethane-organic silicon-acrylic ester polymerization emulsion. The preparation method disclosed by the invention realizes that urethane and organic silicon structures are directly introduced to the molecular structure of polyacrylate, so that the acrylic ester improved through the method not only keeps the inherent advantages of polyacrylate, but also has the advantages of better dry-wet rubbing fastness and more softness in hand feeling in the coating printing finishing of a fabric by effectively utilizing the synergistic effect of two functional materials, namely polyurethane and organic silicon.
Description
Technical field
The invention belongs to textile materials pigment printing technical field, relate to a kind of ternary copolymer emulsion that pigment printing binding agent is used of preparing, ternary copolymer emulsion of especially a kind of urethane, organosilicon and acrylate and preparation method thereof.
Background technology
Chinese Patent Application No. 200310112823.5 proposes the preparation method of polyurethane-acrylate water-dispersed resin, this resin particle is being usingd under the alkene class organosilane monomer of the nucleation condition as medium, the polyurethane prepolymer of first preparing carboxyl group, through in and water-dispersion after generate polyurethane prepolymer, after chain extension, add again polymerisable vinyl monomer, the synthetic water dispersed resin with nucleocapsid structure of radical polymerization under initiator exists; Chinese Patent Application No. 200610096300.X proposes a kind of preparation method of the fluorinated silicone modified polyurethane-acrylate composite emulsion with nucleocapsid structure, comprise and first prepare the hydroxy-end capped organic-silicon-modified water-based aqueous polyurethane dispersion of a kind of alkane, then using polyurethane dispersions as seed emulsion and acrylate and fluorinated acrylate monomer carry out polymerization.In organosilicon polyurethane-acrylic ester polymkeric substance prepared by such seeded emulsion polymerization, most of structure still exists with the form of simple polyacrylic ester and organic silicon modified polyurethane, the resin of this combined state is after film forming, because its structural form is limited, over-all properties still can not be given full play to the features of several resins.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of ammonia ester-organic silicon-acrylate ternary copolymer emulsion and preparation method thereof, the crock fastness that is intended to solve current pigment printing binding agent is not high, the poor problem of fabric sofetening degree after it arranges.
Technical scheme of the present invention is as follows:
A preparation method for ammonia ester-organic silicon-acrylate ternary copolymer emulsion, wherein, described preparation method comprises the following steps:
A, use polyethersiloxanediol modified polyurethane dispersion, then with (methyl) vinylformic acid hydroxyl ester monomer, it is carried out to end-blocking, form two ends with ammonia ester-organic silicon-acrylate polymkeric substance of unsaturated double-bond;
B, resulting ammonia ester-organic silicon-acrylate polymkeric substance and acrylate monomer are carried out to copolymerization, make ammonia ester-Silicone-Acrylic Copolymer Emulsion.
The preparation method of described ammonia ester-organic silicon-acrylate ternary copolymer emulsion, wherein, described steps A is specially:
A1, by polyethers (ester) dibasic alcohol vacuum hydro-extraction 1-2 hour at 100-120 ℃ of temperature of the polyethersiloxanediol of 3-10 part weight part and 2-6 part weight part;
A2, by dehydration after reactant be cooled to 40-50 ℃, add wherein 7-12 part weight part isocyanate-monomer, 0.5-2 part weight part 2, after the chainextender of the solvent of 2-dimethylol propionic acid, 7-12 part weight part, 0.2-0.5 part weight part, be warming up to 75-85 ℃, isothermal reaction 1-3 hour obtains modified polyurethane dispersion;
A3, the modified polyurethane dispersion that reaction is obtained are cooled to 60-65 ℃, drip wherein (methyl) vinylformic acid hydroxyl ester monomer of 3-5 part weight part, at 0.5-1 hour, dropwise, and isothermal reaction 1-2 hour, after finishing, reaction is cooled to 45-55 ℃, the triethylamine reaction 10-30 minute that adds 0.5-2 part weight part, add again the deionized water of 65-72 part weight part and the quadrol of 0.01-0.05 part weight part to carry out emulsification, under vacuum condition, slough solvent afterwards, obtain the ammonia ester-organic silicon-acrylate polymkeric substance that contains unsaturated double-bond.
The preparation method of described ammonia ester-organic silicon-acrylate ternary copolymer emulsion, wherein, described step B is specially:
B1, the anionic emulsifier of the nonionic emulsifying agent of the deionized water of 6-10 part weight part, 0.02-0.05 part weight part, 0.01-0.05 part weight part is mixed to get to bed material liquid;
B2, by ammonia ester-organic silicon-acrylate polymkeric substance of the unsaturated reaction monomers of the acrylate monomer of the nonionogenic tenside of the anion surfactant of 0.03-0.1 part weight part, 0.02-0.2 part weight part, 23-30 part weight part, 5-15 part weight part and 2-15 part weight part, join in the deionized water of 35-45 part weight part, through stirring and emulsifying, obtain pre-emulsion;
B3, the initiator of 0.03-0.1 part weight part is joined in bed material liquid, and then get 1/3 of pre-emulsion total weight parts and add wherein, heating reaches after kick off temperature, initiation reaction 10-30 minute drips remaining pre-emulsion afterwards, and dropwised at 30-120 minute in this reaction solution, 70-85 ℃ of isothermal reaction 30-150 minute afterwards, then be cooled to below 65 ℃, add urea and ammoniacal liquor to adjust pH value to 8.0, filter and obtain ammonia ester-Silicone-Acrylic Copolymer Emulsion.
The preparation method of described ammonia ester-organic silicon-acrylate ternary copolymer emulsion, wherein, described (methyl) vinylformic acid hydroxyl ester monomer is a kind of in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410;
The preparation method of described ammonia ester-organic silicon-acrylate ternary copolymer emulsion, wherein, described acrylate monomer is one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, n-butyl acrylate, isobutyl acrylate, (methyl) Isooctyl acrylate monomer.
The preparation method of described ammonia ester-organic silicon-acrylate ternary copolymer emulsion, wherein, described polyethers (ester) dibasic alcohol is a kind of in polypropylene glycol, polycaprolactone dibasic alcohol, PCDL, PTMG dibasic alcohol.
The preparation method of described ammonia ester-organic silicon-acrylate ternary copolymer emulsion, wherein, described isocyanate-monomer is a kind of in 2,4 toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate;
Described solvent is acetone or butanone;
Described chainextender is BDO, 1, a kind of in 6-hexylene glycol, hydroxymethyl-cyclohexane.
The preparation method of described ammonia ester-organic silicon-acrylate ternary copolymer emulsion, wherein, described nonionic emulsifying agent is that alkyl carbon atoms number is a kind of in the Voranol EP 2001, polyoxyethylene alkyl phenyl ether, polyxyethylated allyl ether of 8 to 16;
The preparation method of described ammonia ester-organic silicon-acrylate ternary copolymer emulsion, wherein, described anion surfactant is a kind of in ammonium lauryl sulfate, Sodium dodecylbenzene sulfonate, hexadecyl benzene sulfonic acid sodium salt;
Described unsaturated reaction monomers is one or more in vinylbenzene, N-methylol methyl acrylate, N-methylol ethyl propenoate, N hydroxymethyl acrylamide, methyl propenoic acid glycidyl ether, vinylformic acid glycidyl ether, vinylformic acid;
Described initiator is water soluble starter, and it is a kind of in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, and kick off temperature is 70-85 ℃.
Ammonia ester-Silicone-Acrylic Copolymer Emulsion, wherein, described ammonia ester-Silicone-Acrylic Copolymer Emulsion utilizes preparation method as above to make.
Beneficial effect: the invention provides a kind of ammonia ester-organic silicon-acrylate ternary copolymer emulsion and preparation method thereof, by the inventive method by ammonia ester, the direct copolymerization of organosilicon structure or be grafted in acrylic ester polymer, thereby realize in polyacrylic ester directly introducing ammonia ester and organosilyl structure on molecular structure.Thereby make ammonia ester-organic silicon-acrylate ternary copolymer emulsion of the present invention not only there is the good cross-linking properties that urethane brings, but also there is the splendid softness that organosilicon brings, therefore the present invention adopts the improved acrylic ester polymer of urethane-organic silicon-acrylate polymkeric substance with unsaturated double-bond, polyacrylic ester inherent advantages have not only been kept, and effectively utilized the synergistic effect of urethane and these two kinds of functional materials of organosilicon, in arranging, textile coating stamp not only there is better dry/fastness to wet rubbing, and feel is more soft.
Embodiment
The invention provides a kind of ammonia ester-organic silicon-acrylate ternary copolymer emulsion and preparation method thereof, for making object of the present invention, technical scheme and effect clearer, clear and definite, below the present invention is described in more detail.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The preparation method who the invention provides a kind of ammonia ester-organic silicon-acrylate ternary copolymer emulsion, wherein, described preparation method comprises the following steps:
A, use polyethersiloxanediol modified polyurethane dispersion, then with (methyl) vinylformic acid hydroxyl ester monomer, it is carried out to end-blocking, form two ends with ammonia ester-organic silicon-acrylate polymkeric substance of unsaturated double-bond.
B, resulting ammonia ester-organic silicon-acrylate polymkeric substance and acrylate monomer are carried out to copolymerization, make ammonia ester-Silicone-Acrylic Copolymer Emulsion.
In preferred embodiment, described steps A is specially:
A1, in one is equipped with the four-hole boiling flask of agitator, reflux exchanger, add the polyethersiloxanediol of 3-10 part weight part and polyethers (ester) dibasic alcohol of 2-6 part weight part, at 100-120 ℃ of temperature, vacuum tightness is at 0.095 above vacuum hydro-extraction 1-2 hour.
Wherein, polyethersiloxanediol specifically adopts polyethersiloxanediol WACKER IM2
(structural formula is HO (CH
2cH
2o)
10cH
2cH
2cH
2[Si (CH
3)
2o]
15si (CH
3)
2cH
2cH
2cH
2
O(CH
2CH
2O)
10?H）。Described polyethers (ester) dibasic alcohol is a kind of in polypropylene glycol, polycaprolactone dibasic alcohol, PCDL, PTMG dibasic alcohol
A2, by dehydration after reactant be cooled to 40-50 ℃, add wherein 7-12 part weight part isocyanate-monomer, 0.5-2 part weight part 2, after the chainextender of the solvent of 2-dimethylol propionic acid, 7-12 part weight part, 0.2-0.5 part weight part, be warming up to 75-85 ℃, isothermal reaction 1-3 hour obtains modified polyurethane dispersion.
Wherein, described isocyanate-monomer is a kind of in 2,4 toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate.Described solvent is acetone or butanone.Described chainextender is BDO, 1, a kind of in 6-hexylene glycol, hydroxymethyl-cyclohexane.
A3, the modified polyurethane dispersion that reaction is obtained is cooled to 60-65 ℃, (methyl) vinylformic acid hydroxyl ester monomer that drips wherein 3-5 part weight part carries out end-blocking, at 0.5-1 hour, dropwise, and isothermal reaction 1-2 hour, after finishing, reaction is cooled to 45-55 ℃, the triethylamine reaction 10-30 minute that adds 0.5-2 part weight part, add again the deionized water of 65-72 part weight part and the quadrol emulsify at a high speed of 0.01-0.05 part weight part, proceed to again Rotary Evaporators, under vacuum condition, slough solvent, obtain the ammonia ester-organic silicon-acrylate polymkeric substance that contains unsaturated double-bond.
Wherein, described (methyl) vinylformic acid hydroxyl ester monomer is a kind of in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410.
In preferred embodiment, described step B is specially:
B1, the anionic emulsifier of the nonionic emulsifying agent of the deionized water of 6-10 part weight part, 0.02-0.05 part weight part, 0.01-0.05 part weight part is mixed to get to bed material liquid.
Wherein, described nonionic emulsifying agent is that alkyl carbon atoms number is a kind of in the Voranol EP 2001, polyoxyethylene alkyl phenyl ether, polyxyethylated allyl ether of 8 to 16.
B2, by ammonia ester-organic silicon-acrylate polymkeric substance of the unsaturated reaction monomers of the acrylate monomer of the nonionogenic tenside of the anion surfactant of 0.03-0.1 part weight part, 0.02-0.2 part weight part, 23-30 part weight part, 5-15 part weight part and 2-15 part weight part, join in the deionized water of 35-45 part weight part, through high-speed stirring emulsification, obtain pre-emulsion.
Wherein, described acrylate monomer is one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, n-butyl acrylate, isobutyl acrylate, (methyl) Isooctyl acrylate monomer.Described anion surfactant is a kind of in ammonium lauryl sulfate, Sodium dodecylbenzene sulfonate, hexadecyl benzene sulfonic acid sodium salt.Described unsaturated reaction monomers is one or more in vinylbenzene, N-methylol methyl acrylate, N-methylol ethyl propenoate, N hydroxymethyl acrylamide, methyl propenoic acid glycidyl ether, vinylformic acid glycidyl ether, vinylformic acid
B3, when bath temperature reaches the kick off temperature of initiator, the initiator that 0.03-0.1 part weight part is reached to kick off temperature joins in bed material liquid, and then get 1/3 of pre-emulsion total weight parts and add wherein, initiation reaction 10-30 minute, in this reaction solution, drip remaining pre-emulsion afterwards, and dropwised at 30-120 minute, continue afterwards 70-85 ℃ of isothermal reaction 30-150 minute, then be cooled to below 65 ℃, add urea and ammoniacal liquor to adjust pH value to 8.0 left and right, filter discharging and obtain ammonia ester-Silicone-Acrylic Copolymer Emulsion.
Wherein, described initiator is water soluble starter, and kick off temperature is 70-85 ℃, concrete, and described initiator is a kind of in ammonium persulphate, Sodium Persulfate, Potassium Persulphate.
The present invention also provides a kind of ammonia ester-Silicone-Acrylic Copolymer Emulsion as pigment printing binding agent, and described ammonia ester-Silicone-Acrylic Copolymer Emulsion utilizes preparation method as above to make.
Below by specific embodiment, further illustrate the solution of the present invention.
Embodiment 1
Component concentration operating weight part in all embodiment of embodiment 1(, unit is gram)
1, the preparation of reactive ammonia ester-organic silicon-acrylate polymkeric substance
One, agitator is housed, the polyethersiloxanediol IM22 that first adds 32g in the four-hole boiling flask of reflux exchanger, the polyether Glycols of 10g (N210), at 100-110 ℃, vacuum tightness is 0.098 vacuum hydro-extraction 2 hours, while being then cooled to 40 ℃, add 30g 2, 4-tolylene diisocyanate (TDI), 2 of 4.5g, 2-dimethylol propionic acid, 30g butanone, 1.2g 1, 4 butyleneglycols, then be warming up to 85 ℃, isothermal reaction 3 hours, after finishing, reaction is cooled to 60 ℃, add 15g hydroxyethyl methylacrylate to carry out end-blocking, at 0.5 hour, dropwise, then isothermal reaction is 2 hours, after finishing, reaction is cooled to 45 ℃, add 3g triethylamine reaction 10 minutes, add again 254g deionized water and 0.8g quadrol, high-speed stirring 20 minutes, proceed to Rotary Evaporators, at 60 ℃, under-0.1MPa vacuum condition, slough butanone, obtain the ammonia ester-organic silicon-acrylate polymer emulsion that contains unsaturated double-bond.
2, the preparation of ammonia ester-organic silicon-acrylate polymkeric substance and acrylate copolymer emulsion
(1) preparation of bed material liquid: by the deionized water of 30g, fatty alcohol-polyoxyethylene ether (the BASF trade mark, AEO-9) Sodium dodecylbenzene sulfonate of 1.2g, 0.8g joins in reactor, reactor is placed in the water-bath with temperature regulating device;
(2) preparation of pre-emulsion: by Sodium dodecylbenzene sulfonate 2g, isomerous tridecanol polyoxyethylene ether (the BASF trade mark, To-7) 3g, n-butyl acrylate 100g, vinylbenzene 36g, N-methylol methyl acrylate 1.8g, containing unsaturated double-bond polymer A 20g, join in the deionized water of 150g, high-speed stirring emulsification forms;
(3) preparation of copolymer emulsion: when bath temperature reaches 75 ℃, the ammonium persulphate of 0.3g is joined in bed material liquid, then getting 1/3 pre-emulsion joins in bed material liquid, after initiation reaction 15 minutes, in bed material liquid, drip remaining pre-emulsion and the initiator ammonium persulfate aqueous solution (ammonium persulphate 0.7g, water is 15g) after within 60 minutes, dropwising, continue 80 ℃ of isothermal reactions 60 minutes, then be cooled to below 65 ℃, add 12g urea and 4.5g ammoniacal liquor to adjust pH value, can make the ternary copolymer emulsion of ammonia ester-silicone-modified polyacrylate.
Embodiment 2
1, the preparation of reactive ammonia ester-organic silicon-acrylate polymkeric substance
One, agitator is housed, the polyethersiloxanediol IM22 that first adds 22g in the four-hole boiling flask of reflux exchanger, the polypropylene glycol PPG-1000 of 20g, at 100-110 ℃, vacuum tightness is 0.098 vacuum hydro-extraction 1.5 hours, while being then cooled to 40 ℃, add 35g isophorone diisocyanate (IPDI), 2 of 4.0g, 2-dimethylol propionic acid, 35g butanone, 1.35g 1, 6 hexylene glycols, then be warming up to 85 ℃, isothermal reaction 3 hours, after finishing, reaction is cooled to 60 ℃, add 14g hydroxyethyl methylacrylate to carry out end-blocking, at 0.5 hour, dropwise, then isothermal reaction is 2 hours, after finishing, reaction is cooled to 45 ℃, add 3g triethylamine reaction 10 minutes, add again 254g deionized water and 0.8g quadrol, high-speed stirring 20 minutes, proceed to Rotary Evaporators, at 60 ℃, under-0.1MPa vacuum condition, slough butanone, obtain reactive ammonia ester-organic silicon-acrylate polymer emulsion.
2, the preparation of ammonia ester-organic silicon-acrylate polymkeric substance and acrylate copolymer emulsion
(1) preparation of bed material liquid: by the deionized water of 30g, isomerous tridecanol polyoxyethylene ether (the BASF trade mark, To-7) Sodium dodecylbenzene sulfonate of 1g, 1g joins in reactor, reactor is placed in the water-bath with temperature regulating device;
(2) preparation of pre-emulsion: by Sodium dodecylbenzene sulfonate 2g, isomerous tridecanol polyoxyethylene ether (the BASF trade mark, To-7) 3g, n-butyl acrylate 80g, Isooctyl acrylate monomer 20g, vinylbenzene 16g, vinylformic acid 3g, N-methylol methyl acrylate 1.5g, containing unsaturated double-bond polymer A 15g, join in the deionized water of 150g, high-speed stirring emulsification forms;
(3) preparation of ternary copolymer emulsion: when bath temperature reaches 75 ℃, the ammonium persulphate of 0.3g is joined in bed material liquid, then getting 1/3 pre-emulsion joins in bed material liquid, after initiation reaction 15 minutes, in bed material liquid, drip remaining pre-emulsion and the initiator ammonium persulfate aqueous solution (ammonium persulphate 0.7g, water is 15g) after within 60 minutes, dropwising, continue 75 ℃ of isothermal reactions 60 minutes, then be cooled to below 65 ℃, add 12g urea and 4.5g ammoniacal liquor to adjust pH value, filter discharging, obtain reactive ammonia ester-organic silicon-acrylate polymer emulsion.
Embodiment 3
1, the preparation of reactive ammonia ester-organic silicon-acrylate polymkeric substance
One, agitator is housed, the polyethersiloxanediol IM22 that first adds 27g in the four-hole boiling flask of reflux exchanger, the PCDL PCD of 15g, at 100-110 ℃, vacuum tightness is 0.098 vacuum hydro-extraction 1 hour, while being then cooled to 40 ℃, add 35g diphenylmethanediisocyanate MDI, 2 of 3.5g, 2-dimethylol propionic acid, 30g acetone, 1g 1, 4 butyleneglycols, then be warming up to 85 ℃, isothermal reaction 4 hours, after finishing, reaction is cooled to 60 ℃, add 16g hydroxyethyl methylacrylate to carry out end-blocking, at 0.5 hour, dropwise, then isothermal reaction is 2 hours, after finishing, reaction is cooled to 45 ℃, add 3g triethylamine reaction 10 minutes, add again 254g deionized water and 0.8g quadrol, high-speed stirring 20 minutes, proceed to Rotary Evaporators, at 60 ℃, under-0.1MPa vacuum condition, slough butanone, obtain reactive polyurethane-organic silicon-acrylate polymer emulsion.
2, the preparation of reactive polyurethane-organic silicon-acrylate polymkeric substance and acrylate copolymer emulsion
(1) preparation of bed material liquid: by the deionized water of 30g, isomerous tridecanol polyoxyethylene ether (the BASF trade mark, To-7) the hexadecyl benzene sulfonic acid sodium salt of 0.8g, 1.2g joins in reactor, reactor is placed in the water-bath with temperature regulating device;
(2) preparation of pre-emulsion: by hexadecyl benzene sulfonic acid sodium salt 2g, isomerous tridecanol polyoxyethylene ether (the BASF trade mark, To-7) 2.4g, isobutyl acrylate 90g, vinylbenzene 25g, methyl methacrylate 20g, N-methylol methyl acrylate 2.5g, containing unsaturated double-bond polymer A 20g, join in the deionized water of 150g, high-speed stirring emulsification forms;
(3) preparation of ternary copolymer emulsion: when bath temperature reaches 75 ℃, the ammonium persulphate of 0.3g is joined in bed material liquid, then getting 1/3 pre-emulsion joins in bed material liquid, after initiation reaction 15 minutes, in bed material liquid, drip remaining pre-emulsion and the initiator ammonium persulfate aqueous solution (ammonium persulphate 0.7g, water is 15g) after within 60 minutes, dropwising, continue 85 ℃ of isothermal reactions 60 minutes, then be cooled to below 65 ℃, add 14g urea and 4g ammoniacal liquor to adjust pH value, filter discharging, obtain reactive ammonia ester-organic silicon-acrylate polymer emulsion.
Embodiment 4
Embodiment 4 is comparative example, and preparation is not containing urethane-organosilyl polyacrylate dispersion
Urethane-organic silicon-acrylate polymkeric substance in embodiment 1 is replaced with to 2g hydroxyethyl methylacrylate, 3g vinylformic acid, the 150g deionized water using in pre-emulsion preparation process in embodiment 1 is replaced with to 165g deionized water, all the other raw materials and content, reaction conditions etc. are all constant, specific as follows:
(1) preparation of bed material liquid: by the fatty alcohol-polyoxyethylene ether of the deionized water of 30g, 1.2g (the BASF trade mark, AEO-9), the Sodium dodecylbenzene sulfonate of 0.8g joins in reactor, reactor is placed in the water-bath with temperature regulating device;
(2) preparation of pre-emulsion: by Sodium dodecylbenzene sulfonate 2g, isomerous tridecanol polyoxyethylene ether (the BASF trade mark, To-7) 3g, n-butyl acrylate 100g, vinylbenzene 36g, N-methylol methyl acrylate 1.8g, hydroxyethyl methylacrylate 3g, vinylformic acid 2g, join in the deionized water of 165g, high-speed stirring emulsification forms;
(3) preparation of ternary copolymer emulsion: when bath temperature reaches 75 ℃, the ammonium persulphate of 0.3g is joined in bed material liquid, then getting 1/3 pre-emulsion joins in bed material liquid, after initiation reaction 15 minutes, in bed material liquid, drip remaining pre-emulsion C and the initiator ammonium persulfate aqueous solution (ammonium persulphate 0.7g, water is 15g) after within 60 minutes, dropwising, continue 80 ℃ of isothermal reactions 60 minutes, then be cooled to below 65 ℃, make comparative example emulsion after adding 12g urea and 4.5g ammoniacal liquor to adjust pH value.
Performance Ratio is:
The emulsion making is mixed with coating, thickening material and water respectively, according to stamp, dries (100 ℃ * 3 minutes), bake (150 ℃ * 3 minutes), then according to doing according to GB/T 3920-1997 standard, fastness to wet rubbing measures.According to GB251-1984 standard, at the D of standard light both
65under light source, the gray card that operational evaluation staining is used is evaluated staining fabric.Soft type test adopts hand feel evaluation method, selects by certain experiences, 5 people that feel is sensitive and forms evaluation group, to close order sense of touch, evaluates, and 5 grades for the highest, and 1 grade is minimum.Test result is in Table 1:
Table 1
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Dry fastness | 5 | 5 | 5 | 4 |
| Fastness to wet rubbing | 3.5~4 | 3.5 | 3.5~4 | 2.5 |
| Pliability | 5 | 4 | 4 | 3 |
As can be seen from Table 1, using urethane-Silicone-Acrylic Copolymer Emulsion as the more general palyacrylate binder of pigment printing binding agent, it is dry, fastness to wet rubbing has obvious lifting, and its feel is also better soft.
The invention provides a kind of ammonia ester-organic silicon-acrylate ternary copolymer emulsion and preparation method thereof, by the inventive method by ammonia ester, the direct copolymerization of organosilicon structure or be grafted in acrylic ester polymer, thereby realize in polyacrylic ester directly introducing ammonia ester and organosilyl structure on molecular structure.Thereby make ammonia ester-organic silicon-acrylate ternary copolymer emulsion of the present invention not only there is the good cross-linking properties that urethane brings, but also there is the splendid softness that organosilicon brings, therefore the present invention adopts with the acrylate after urethane-organic silicon-acrylate polymkeric substance improvement of unsaturated double-bond, polyacrylic ester inherent advantages have not only been kept, and effectively utilized the synergistic effect of urethane and these two kinds of functional materials of organosilicon, in arranging, textile coating stamp not only there is better dry/fastness to wet rubbing, and feel is more soft.
Should be understood that, application of the present invention is not limited to above-mentioned giving an example, and for those of ordinary skills, can be improved according to the above description or convert, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (10)
1. a preparation method for ammonia ester-organic silicon-acrylate ternary copolymer emulsion, is characterized in that, described preparation method comprises the following steps:
A, use polyethersiloxanediol modified polyurethane dispersion, then with (methyl) vinylformic acid hydroxyl ester monomer, it is carried out to end-blocking, form two ends with ammonia ester-organic silicon-acrylate polymkeric substance of unsaturated double-bond;
B, resulting ammonia ester-organic silicon-acrylate polymkeric substance and acrylate monomer are carried out to copolymerization, make ammonia ester-Silicone-Acrylic Copolymer Emulsion.
2. the preparation method of ammonia ester-organic silicon-acrylate ternary copolymer emulsion according to claim 1, is characterized in that, described steps A is specially:
A1, by polyethers (ester) dibasic alcohol vacuum hydro-extraction 1-2 hour at 100-120 ℃ of temperature of the polyethersiloxanediol of 3-10 part weight part and 2-6 part weight part;
A2, by dehydration after reactant be cooled to 40-50 ℃, add wherein 7-12 part weight part isocyanate-monomer, 0.5-2 part weight part 2, after the chainextender of the solvent of 2-dimethylol propionic acid, 7-12 part weight part, 0.2-0.5 part weight part, be warming up to 75-85 ℃, isothermal reaction 1-3 hour obtains modified polyurethane dispersion;
A3, the modified polyurethane dispersion that reaction is obtained are cooled to 60-
65 ℃, drip wherein (methyl) vinylformic acid hydroxyl ester monomer of 3-5 part weight part, at 0.5-1 hour, dropwise, and isothermal reaction 1-2 hour, after reaction finishes, be cooled to 45-55 ℃, add the triethylamine reaction 10-30 minute of 0.5-2 part weight part, then add the deionized water of 65-72 part weight part and the quadrol of 0.01-0.05 part weight part to carry out emulsification, under vacuum condition, slough solvent afterwards, obtain the ammonia ester-organic silicon-acrylate polymkeric substance that contains unsaturated double-bond.
3. the preparation method of ammonia ester-organic silicon-acrylate ternary copolymer emulsion according to claim 2, is characterized in that, described step B is specially:
B1, the anionic emulsifier of the nonionic emulsifying agent of the deionized water of 6-10 part weight part, 0.02-0.05 part weight part, 0.01-0.05 part weight part is mixed to get to bed material liquid;
B2, by ammonia ester-organic silicon-acrylate polymkeric substance of the unsaturated reaction monomers of the acrylate monomer of the nonionogenic tenside of the anion surfactant of 0.03-0.1 part weight part, 0.02-0.2 part weight part, 23-30 part weight part, 5-15 part weight part and 2-15 part weight part, join in the deionized water of 35-45 part weight part, through stirring and emulsifying, obtain pre-emulsion;
B3, the initiator that 0.03-0.1 part weight part is reached to kick off temperature join in bed material liquid, and then get 1/3 of pre-emulsion total weight parts and add wherein, heating reaches after kick off temperature, initiation reaction 10-30 minute, in this reaction solution, drip remaining pre-emulsion afterwards, and dropwised at 30-120 minute, 70-85 ℃ of isothermal reaction 30-150 minute afterwards, then be cooled to below 65 ℃, add urea and ammoniacal liquor to adjust pH value to 8.0, filter and obtain ammonia ester-Silicone-Acrylic Copolymer Emulsion.
4. the preparation method of ammonia ester-organic silicon-acrylate ternary copolymer emulsion according to claim 3, it is characterized in that, described (methyl) vinylformic acid hydroxyl ester monomer is a kind of in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410.
5. the preparation method of ammonia ester-organic silicon-acrylate ternary copolymer emulsion according to claim 3, it is characterized in that, described acrylate monomer is one or more in (methyl) methyl acrylate, (methyl) ethyl propenoate, n-butyl acrylate, isobutyl acrylate, (methyl) Isooctyl acrylate monomer.
6. the preparation method of ammonia ester-organic silicon-acrylate ternary copolymer emulsion according to claim 3, it is characterized in that, described polyethers (ester) dibasic alcohol is a kind of in polypropylene glycol, polycaprolactone dibasic alcohol, PCDL, PTMG dibasic alcohol.
7. the preparation method of ammonia ester-organic silicon-acrylate ternary copolymer emulsion according to claim 3, it is characterized in that, described isocyanate-monomer is 2, a kind of in 4-tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate;
Described solvent is acetone or butanone;
Described chainextender is BDO, 1, a kind of in 6-hexylene glycol, hydroxymethyl-cyclohexane.
8. the preparation method of ammonia ester-organic silicon-acrylate ternary copolymer emulsion according to claim 3, it is characterized in that, described nonionic emulsifying agent is that alkyl carbon atoms number is a kind of in the Voranol EP 2001, polyoxyethylene alkyl phenyl ether, polyxyethylated allyl ether of 8 to 16.
9. the preparation method of ammonia ester-organic silicon-acrylate ternary copolymer emulsion according to claim 3, is characterized in that, described anion surfactant is a kind of in ammonium lauryl sulfate, Sodium dodecylbenzene sulfonate, hexadecyl benzene sulfonic acid sodium salt;
Described unsaturated reaction monomers is one or more in vinylbenzene, N-methylol methyl acrylate, N-methylol ethyl propenoate, N hydroxymethyl acrylamide, methyl propenoic acid glycidyl ether, vinylformic acid glycidyl ether, vinylformic acid;
Described initiator is water soluble starter, and it is a kind of in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, and kick off temperature is 70-85 ℃.
10. ammonia ester-Silicone-Acrylic Copolymer Emulsion, is characterized in that, the utilization of described ammonia ester-Silicone-Acrylic Copolymer Emulsion is the preparation method as described in claim 1-9 any one make.
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